Catalytic Enantioselective Construction of Chiroptical Boron-Stereogenic Compounds

Zu, Bing1,2,3; Guo, Yonghong2,3; He, Chuan2,3

2021-10-06

10.1021/jacs.1c08482

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

The construction of main group heteroatom-stereogenic compounds is of great importance due to their intriguing chemical, physical, biological, and stereoelectronic properties. Despite that organoboron compounds are widely used in organic chemistry, the creation of a tetrahedral boron-stereogenic center in one enantiomeric form remains highly challenging. Given the labile nature of ligands attached to the tetracoordinate boron atom, only a handful of enantioenriched boron-stereogenic compounds have been reported via resolution or a chiral substrate- induced diastereoselective approach. To date catalytic asymmetric synthesis of boron-stereogenic compounds has remained unknown. Here, we demonstrate the first catalytic enantioselective construction of boron-stereogenic compounds via an asymmetric copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. This enantioselective CuAAC reaction not only gives access to a wide range of novel highly functionalized boron-stereogenic heterocycles in high yields with good to excellent enantioselectivities but also produces optically active terminal alkyne and triazole moieties with various potential application prospects. Further transformation of the chiral tetracoordinate boron compounds delivers several complex heterocyclic entities bearing boron-stereogenic centers without the loss of enantiopurity. Moreover, the X-ray structure, the barrier to racemization, and the HOMO/LUMO gap of selected tetracoordinate boron compounds are investigated. Notably, these novel N,N pi-conjugated boron-stereogenic compounds exhibit bright fluorescence. The optical properties, including circular dichroism, quantum yield, and circular polarized luminescence spectroscopies, are examined. These features expand the chemical space of the chiroptical boron-based dye platform, which could have great potential applications in chiral optoelectronic materials.

SCI ; EI

英语

NI论文

通讯

National Natural Science Foundation of China[21901104] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Science and Technology Innovation Committee[JCYJ20190809142809370] ; Stable Support Plan Program of Shenzhen Natural Science Fund[20200925152450004]

Chemistry

Chemistry, Multidisciplinary

WOS:000706193200041

AMER CHEMICAL SOC

20214211039975

Copper compounds ; Cycloaddition ; Dichroism ; Hydrocarbons ; Optoelectronic devices ; Stereochemistry

Light/Optics:741.1 ; Optical Devices and Systems:741.3 ; Chemistry:801 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1

Web of Science

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150080, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Guangdong, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China

Zu, Bing,Guo, Yonghong,He, Chuan. Catalytic Enantioselective Construction of Chiroptical Boron-Stereogenic Compounds[J]. Journal of the American Chemical Society,2021,143(39):16302-16310.

Zu, Bing,Guo, Yonghong,&He, Chuan.(2021).Catalytic Enantioselective Construction of Chiroptical Boron-Stereogenic Compounds.Journal of the American Chemical Society,143(39),16302-16310.

Zu, Bing,et al."Catalytic Enantioselective Construction of Chiroptical Boron-Stereogenic Compounds".Journal of the American Chemical Society 143.39(2021):16302-16310.